JP2004124069A - Silica-coated aluminum pigment and its production method as well as application thereof - Google Patents

Silica-coated aluminum pigment and its production method as well as application thereof Download PDF

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Publication number
JP2004124069A
JP2004124069A JP2003202191A JP2003202191A JP2004124069A JP 2004124069 A JP2004124069 A JP 2004124069A JP 2003202191 A JP2003202191 A JP 2003202191A JP 2003202191 A JP2003202191 A JP 2003202191A JP 2004124069 A JP2004124069 A JP 2004124069A
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Japan
Prior art keywords
silica
aluminum pigment
aluminum
film
coated aluminum
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Pending
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JP2003202191A
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Japanese (ja)
Inventor
Nobuaki Ishii
Shuichi Nishikawa
Yasuo Saito
Koichi Wada
和田 紘一
斉藤 康夫
石井 伸晃
西川 修一
Original Assignee
Showa Aluminum Powder Kk
Showa Denko Kk
昭和アルミパウダー株式会社
昭和電工株式会社
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Application filed by Showa Aluminum Powder Kk, Showa Denko Kk, 昭和アルミパウダー株式会社, 昭和電工株式会社 filed Critical Showa Aluminum Powder Kk
Priority to JP2003202191A priority patent/JP2004124069A/en
Publication of JP2004124069A publication Critical patent/JP2004124069A/en
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum pigment solving problems of conventional aluminum pigments such as generation of hydrogen when it is formulated in a water-based paint or water-based ink, deterioration of gloss, thickening when it is formulated in a coating, gelling phenomenon and lowering of electric strength. <P>SOLUTION: This silica-coated aluminum pigment is the one in which an aluminum particle is coated with a silica multilayered film where a silica thin film of 0.5 to 5 nm thickness is formed in multilayers on the surface of the aluminum particle. The production method of the silica-coated aluminum pigment comprises a step of dispersing aluminum particles in a solution containing a hydrolyzing catalyst, water and a hydrophilic organic solvent, and a step of adding a solution containing an Si-containing compound to the dispersion at a maximum silica film deposition rate of ≤3 nm/hr. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to aluminum pigments using aluminum particles. More specifically, when blended in a water-based paint or water-based ink, there is no gas generation and excellent storage stability, or when blended in a paint or ink, the composition does not gel and has a long storage stability. The present invention relates to an aluminum pigment having excellent heat resistance. Further, the present invention relates to an aluminum pigment which satisfies the voltage resistance without impairing the metallic feeling when blended in a metallic paint for forming a coating film requiring the voltage resistance.
[0002]
[Prior art]
Many techniques have been disclosed for aluminum pigments incorporated in water-based paints. For example, JP-A-10-130545 (Patent Document 1) discloses a method of processing an aluminum pigment with inorganic phosphoric acid, an inorganic phosphate, a phosphate compound, or the like. Further, Japanese Patent Application Laid-Open No. 62-81460 (Patent Document 2) discloses a method of coating a resin on an aluminum surface. Japanese Patent Application Laid-Open No. 2002-121423 (Patent Document 3) discloses a method of further subjecting a resin-coated aluminum pigment to a chemical conversion treatment, and Japanese Patent Application Laid-Open No. 2002-88274 (Patent Document 4) contains phosphorus. A method of coated silica coating is disclosed. JP-A-7-3185 (Patent Document 5) discloses a method in which a siloxane coating is applied to the surface of an aluminum pigment, and a synthetic resin coating is further formed. JP-A-57-42772 (Patent Document 6) discloses a method in which an aluminum pigment is dispersed in soluble silicic acid adjusted to a pH of 10.0 to 10.8 to prepare a pigment colored brown or black. However, in these methods, it is necessary to obtain an aluminum pigment excellent in storage stability in water-based paints, storage stability in heat-curable and energy-ray-curable paints, and withstand voltage and gloss of coating films. Is difficult at present.
[0003]
In Japanese Patent Application Laid-Open No. 2002-88274 (Patent Document 7), a fine particle of 0.01 μm or less adheres to the surface of a phosphorus-containing silica film to form a coating, thereby improving the denseness of the film. However, it is disclosed that only a silica film containing no phosphorus has poor water resistance and generates a large amount of hydrogen.
[0004]
Patent Literature 6 aims at improving selective absorbability to sunlight by coloring an aluminum pigment, and does not describe a water-based paint or the like.
[0005]
In Patent Document 5, a siloxane coating equivalent to a monomolecular layer is applied to an aluminum pigment to improve the adhesion and sealing properties between the resin and the aluminum pigment. A barrier property is a problem with only a siloxane coating equivalent to a monomolecular layer.
[Patent Document 1]
JP-A-10-130545
[Patent Document 2]
JP-A-62-81460
[Patent Document 3]
JP 2002-121423 A
[Patent Document 4]
JP 2002-88274 A
[Patent Document 5]
JP-A-7-3185
[Patent Document 6]
JP-A-57-42772
[Patent Document 7]
JP 2002-88274 A
[0006]
[Problems to be solved by the invention]
Aluminum pigments have the property of reacting with the water contained in them to generate and dissolve hydrogen gas when blended into water-based paints and water-based inks, especially in water-based paints and inks with a high pH value. Notable.
[0007]
Further, when the aluminum pigment is added to a heat-curable or ultraviolet ray-curable energy ray-curable paint or ink, the paint or ink may thicken or gel. Although the reaction mechanism of this phenomenon has not been elucidated, it seems that the metal surface of aluminum is involved in some way.
[0008]
Furthermore, when the withstand voltage of the coating film is required at a portion applied to an electric appliance or the like, the withstand voltage required for the conductivity of aluminum is not satisfied by the paint containing the conventional aluminum pigment. There is also a problem.
[0009]
An object of the present invention is to provide an aluminum pigment that solves the above problems.
[0010]
[Means for Solving the Problems]
The present inventor has conducted intensive studies on the above problems, and as a result, has found that the above problem can be solved by providing a multilayer film of a silica thin film which is a dense continuous film on the surface of aluminum particles. Invented.
[0011]
That is, the present invention
1) A silica-coated aluminum pigment, wherein a silica thin film having a thickness of 0.5 to 5 nm is formed in multiple layers on the surface of aluminum particles.
2) The silica-coated aluminum pigment according to 1 above, wherein the aluminum pigment has an aluminum oxide layer between the surface of the aluminum particles and the silica thin film.
3) The silica-coated aluminum pigment according to 1 or 2 above, wherein the silica multilayer film in which the silica thin film is formed in multiple layers has a thickness of 3 to 30 nm.
4) The volume of hydrogen gas generated from 1 g of aluminum in the aluminum pigment at a temperature of 50 ° C. for 336 hours is 1 cm. 3 4. The silica-coated aluminum pigment according to any one of the above items 1 to 3, wherein
5) When mixed with the water-based paint or water-based ink at 50 ° C. for 336 hours, the volume of hydrogen gas generated from 1 g of aluminum in the aluminum pigment is 10 cm. 3 4. The silica-coated aluminum pigment according to any one of the above items 1 to 3, wherein
6) 1150-1250 cm of the silica multilayer film -1 And 1000-1100cm -1 Ratio of the absorption peak intensities in the infrared absorption spectrum I (I = I 1 / I 2 : I 1 Is 1150-1250cm -1 Absorption peak intensity, I 2 Is 1000-1100cm -1 The silica-coated aluminum pigment according to any one of the above items 1 to 5, wherein the absorption peak intensity is 0.2 or more, and the refractive index of the silica film is 1.435 or more.
7) The silica-coated aluminum pigment according to any one of 1 to 6 above, wherein the amount of Si element in the silica multilayer film is 1 to 10% by mass with respect to aluminum in the aluminum particles.
8) The silica-coated aluminum pigment according to any one of 1 to 7 above, wherein the surface of the silica multilayer film is hydrophobized with a hydrophobicity-imparting agent.
9) The silica-coated aluminum pigment according to 8 above, wherein the hydrophobicity imparting agent is at least one selected from a silane-based coupling agent, an aluminum-based coupling agent, and a titanate-based coupling agent.
10) The silica-coated aluminum pigment according to any one of 1 to 9 above, wherein the aluminum particles are flake-like particles.
11) The silica-coated aluminum pigment according to any one of 1 to 9 above, wherein the aluminum particles are flake-like particles, the average particle diameter D50 is 5 to 100 μm, and the aspect ratio (particle diameter / thickness) is 20 or more.
12) a step of dispersing aluminum particles in a solution containing a hydrolysis catalyst, water and a hydrophilic organic solvent, and a step of adding a solution containing a Si-containing compound to the dispersion so that the maximum deposition rate of the silica film is 3 nm / hr or less. A method for producing a silica-coated aluminum pigment comprising:
13) A step of dispersing aluminum particles in a solution containing a Si-containing compound, water and a hydrophilic organic solvent, and a step of adding a solution containing a hydrolysis catalyst to the dispersion so that the maximum deposition rate of the silica film is 3 nm / hr or less. A method for producing a silica-coated aluminum pigment comprising:
(14) The method for producing a silica-coated aluminum pigment according to the above (12) or (13), comprising a step of heating the silica-coated aluminum pigment in a solution containing an organic solvent having a boiling point of 70 ° C. or higher.
15) The method for producing a silica-coated aluminum pigment according to any one of the above items 12 to 14, wherein the Si-containing compound is a compound capable of hydrolyzing in the presence of a hydrolysis catalyst to produce silica.
16) The method for producing a silica-coated aluminum pigment according to the above 15, wherein the Si-containing compound is a silicon alkoxide.
17) The silica-coated aluminum pigment according to 16 above, wherein the silicon alkoxide is at least one selected from tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Manufacturing method.
18) The silica according to any one of the above items 12 to 14, wherein the hydrolysis catalyst is at least one selected from ammonia, ethylenediamine, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, sodium carbonate and sodium bicarbonate. A method for producing a coated aluminum pigment.
19) A paste containing the silica-coated aluminum pigment according to any one of the above 1 to 11.
20) An aqueous paste containing the silica-coated aluminum pigment described in any one of 1 to 11 above and water.
21) A coating film containing the silica-coated aluminum pigment according to any one of the above 1 to 11.
22) A coating containing the silica-coated aluminum pigment according to any one of the above 1 to 11.
23) An ink composition containing the silica-coated aluminum pigment described in any one of 1 to 11 above.
24) A painted article to which the paint described in 22 above is applied.
25) A printed material using the ink composition described in 23 above.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The outline of the method for producing the aluminum pigment coated with the silica multilayer film of the present invention will be described. First, aluminum particles (raw aluminum pigment) are dispersed in a hydrophilic organic solvent, water, and a hydrolysis catalyst, a Si-containing compound for forming a silica thin film is added, and a silica-forming reaction is performed by hydrolysis of the Si-containing compound. A multi-layered silica thin film is formed on the surface of the aluminum particles and covered with the silica multi-layer film. The aluminum pigment coated with the silica film after the reaction can be converted into a pigment or a pigment paste through filtration, solvent washing, drying operation and the like. Further, by dehydrating and condensing the silica film, the pigment paste can be dispersed in a high-boiling-point solvent and heated to improve the barrier property. Aluminum pigments are based on aluminum particles.
[0013]
The aluminum particles used in the present invention can be obtained by directly pulverizing aluminum, mechanical pulverization, or vapor deposition of aluminum. As the mechanical pulverization, those produced by a method such as a ball mill pulverization method, a stamp mill method, an attritor method, a vibration mill or a vapor deposition method can be suitably used. Further, the aluminum particles may be composed only of aluminum, or may be composed of an alloy based on aluminum, and the purity thereof is not particularly limited.
[0014]
Examples of the shape of the aluminum particles include a teardrop shape, a spherical shape, a needle shape, an irregular shape, and a flake (scale) shape. When used as a metallic paint, the flake shape is preferable, and the average particle size (D50: cumulative It is preferable that the thickness is 1 μm or less and the aspect ratio (particle diameter / thickness) is 20 or more. Further, the aspect ratio is preferably 1000 or less. If it exceeds 1,000, the mechanical strength of the pigment may decrease, and the color tone may become unstable.
[0015]
The average particle diameter of the aluminum particles is determined by calculating a volume average from a particle size distribution measured by a known particle size distribution measuring method such as a laser diffraction method, a micromesh sieve method, a Coulter counter method, or the like.
[0016]
Further, a grinding aid may be attached to the surface of the aluminum particles. Unsaturated fatty acids are usually used as grinding aids. The unsaturated fatty acids used herein include, for example, oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid, myristic acid, linoleic acid, linoleic acid, ricinoleic acid, elaidic acid, zomalic acid, gadolinic acid, elka Acids and the like.
When the aluminum pigment is made into a dry powder, it is usually in the form of a paste containing a solvent due to the danger of dust explosion and difficulty in handling. In the present invention, the aluminum pigment may be used as it is, or may be used after washing to remove the solvent. When using an aluminum paste containing a hydrophobic organic solvent such as mineral spirits, a nonionic or anionic surfactant may be added to facilitate emulsification and dispersion in water.
[0017]
The hydrophilic organic solvent for dispersing the aluminum particles is not particularly limited as long as it has an affinity for water and forms a uniform solution. Preferred examples include glycols and alcohols. Alternatively, two or more kinds can be used. Examples of glycols include propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol, propylene glycol, diethylene glycol, and the like. Examples of the alcohols include methanol, ethanol, isopropyl alcohol, butanol, and pentanol. Among these, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and ethanol are particularly preferable from the viewpoint of dispersibility of the aluminum pigment. One of these organic solvents may be used alone, or two or more of them may be used in combination. The hydrophilic organic solvent used in the present invention is not particularly limited, and may be one that is widely used for industrial purposes or as a reagent. Preferably, a higher-purity solvent is suitable.
[0018]
As the Si-containing compound used for coating with the silica thin film, any compound that hydrolyzes to produce silica can be used, but silicon alkoxide is preferable. The silicon alkoxide is not particularly limited, and may be one widely used for industrial purposes or widely as a reagent, and preferably has higher purity. General formula Si- (OR) 4 (R represents a hydrocarbon group such as a C1 to C5 alkyl group, and R may be all the same or different, or may partially include different ones) or an alkoxy group. A partially substituted alkyl group can also be used. Specifically, there are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and the like. The silicon alkoxide may be a monomer, an oligomer, or a mixture thereof. Further, among the Si-containing compounds used for coating with the silica thin film of the present invention, among them, tetraethoxysilane having an appropriate hydrolysis rate is particularly preferably used. The Si-containing compounds may be used alone or in combination of two or more.
[0019]
The amount of silicon alkoxide to be used cannot be unconditionally defined because it varies depending on the type of aluminum particles used. It is desirable to set the amount to be used so as to be at most 2% by mass, more preferably 2 to 4% by mass.
[0020]
When the amount of silicon alkoxide used is small, the barrier properties of the silica multilayer film are insufficient, and particularly when applied to water-based paints, the amount of hydrogen gas generated increases. If the amount of the silicon alkoxide is too large, silica is excessively adhered to the surface of the aluminum particles, and the metallic luster of the aluminum particles may be impaired. Further, if a silica coating of 10% by mass or more in terms of Si atoms is formed on aluminum, the metallic luster (metallic feeling) of the aluminum pigment is undesirably deteriorated.
[0021]
The thickness of the silica thin film is silica (SiO 2 ) One or more layers of molecules may be used, but it is 0.5 to 5 nm, preferably 0.5 to 3 nm. The silica thin film may cover at least a part of the surface of the aluminum particles, and the silica thin films may overlap each other to form a multilayer state, and the multilayer silica film may eventually cover the entire surface of the aluminum particles. The silica multilayer film may be uniform or non-uniform in thickness and may be a dense (high density, defect-free) continuous film.
[0022]
The aluminum particles are in a state of aluminum metal on the surface, in a state where the surface is oxidized and has an aluminum oxide layer, and in a state where the protective film is made of a fatty acid such as stearyl acid to prevent the generation of an aluminum hydroxide film. There may be.
[0023]
The thickness of the silica multilayer film is determined by the balance between barrier properties and metallic luster, and is preferably 3 to 30 nm, more preferably 5 to 15 nm. The silica multilayer thickness can be determined from a transmission electron microscope image.
[0024]
When a silicon alkoxide is used as the Si-containing compound, for example, aluminum particles and a dispersion containing the silicon alkoxide are hydrolyzed by adding water or a hydrolysis catalyst to the silicon alkoxide to deposit a silica coating on the aluminum pigment surface. be able to. The hydrolysis rate is adjusted by the molar ratio and the concentration of the water used with the silicon alkoxide and the molar ratio and the concentration of the hydrolysis catalyst with the silicon alkoxide. The silicon alkoxide is hydrolyzed to form a silanol -OH group, which undergoes a condensation reaction with the -OH group and the like on the surface of the aluminum particles, and a Si-O-Si bond can be formed by a polymerization reaction of the silicon alkoxide. It is considered that a silica coating is formed on the surface.
[0025]
The hydrolysis catalyst for hydrolyzing the Si-containing compound used in the present invention is not particularly limited, for example, ammonia, inorganic alkalis such as sodium hydroxide and potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, Inorganic alkali salts such as sodium hydrogen carbonate, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, ethylenediamine, organic alkalis such as pyridine, aniline, choline, tetramethylammonium hydroxide, guanidine, ammonium formate, ammonium acetate And organic acid alkali salts such as monomethylamine formate, dimethylamine acetate, pyridine lactate, guanidinoacetic acid and aniline acetate. In particular, ammonia, ethylenediamine, ammonium carbonate, ammonium hydrogen carbonate, ammonium formate, ammonium acetate, sodium carbonate, and sodium hydrogen carbonate are preferred. One of these hydrolysis catalysts may be used alone, or two or more thereof may be used in combination.
The hydrolysis catalyst used in the present invention is not particularly limited, and may be one that is widely used for industrial purposes or as a reagent, but preferably has higher purity.
[0026]
The water used in the composition for forming a silica film in the present invention is not particularly limited, and is preferably water from which particles have been removed by filtration or the like. If particles are contained in the water, they are mixed in the product as impurities, which is not preferable.
[0027]
Water can be used in an organic solvent / water ratio of 0 to 10 (0 indicates water only) by volume. If the ratio is out of this range, the film may not be formed, or the film forming speed may be extremely reduced. More preferably, the ratio of organic solvent / water is in the range of 2-5. When the ratio of the organic solvent / water is in the range of 2 to 5, the type of the hydrolysis catalyst to be used is not limited. If the ratio deviates from this, that is, if the ratio of organic solvent / water is less than 2, a film can be formed by using a hydrolysis catalyst containing no alkali metal, such as ammonia, ethylenediamine, ammonium hydrogen carbonate, or ammonium carbonate.
[0028]
To increase the film formation rate, it is effective to increase the film formation temperature. In this case, it is preferable to use a hydrolysis catalyst and an organic solvent which are not easily volatilized and decomposed at the film formation temperature. For example, in the case of sodium carbonate, a small amount of about 0.002 mol / L can be used to form a film, but a large amount of about 1 mol / L may be added. However, if the solid alkali is added in an amount that does not dissolve, it is not preferable because it is mixed as an impurity into the aluminum pigment. If necessary, a silica coating having a low alkali metal content can be formed by using a hydrolysis catalyst containing no alkali metal as a main component. Among them, ammonia, ethylenediamine, and inorganic ammonium salts (for example, ammonium carbonate and ammonium hydrogencarbonate) are particularly preferable from the viewpoint of the film formation rate and the ease of removing the residue.
[0029]
The composition for forming a silica film of the present invention can be prepared by a general solution preparation method. For example, after adding a predetermined amount of hydrolysis catalyst and water to an organic solvent and stirring, silicon alkoxide is added and stirred, and the like. It is possible. Preferably, aluminum particles are added to a predetermined amount of a hydrolysis catalyst and water in an organic solvent, and silicon alkoxide is added to the stirred dispersion. When mixing the silicon alkoxide, dilution with an organic solvent is preferable in terms of controllability of the hydrolysis reaction.
[0030]
A method for producing an aluminum pigment coated with a silica multilayer film using the composition for forming a silica film of the present invention will be described.
Basically, a silica coating can be formed by immersing aluminum particles in a composition for forming a silica coating and maintaining the aluminum particles at a predetermined temperature. A method for preparing a silica film-forming composition in advance and adding aluminum particles therein to deposit a silica film, a method for preparing an aluminum particle in a container and preparing the silica film-forming composition there, etc. Can be used. Regardless of the order in which the composition raw material for forming a silica film and the aluminum particles are charged, the film can be formed in any order. Here, the present inventors formed a suspension or a dispersion liquid with aluminum particles, an organic solvent, water and a hydrolysis catalyst, and then, when tetraalkoxysilane was added over time, a dense silica coating film was formed. It has been found that this makes it possible to construct an industrially useful continuous process.
Since the silica coating grows by deposition on the surface of the aluminum particles, the film thickness can be increased by increasing the deposition time. Of course, when the silicon alkoxide in the film-forming composition is mostly consumed by the formation of the film, the film formation rate is significantly reduced. Thus, the film can be deposited at a practical film forming speed. Further, if a silicon alkoxide component (a silicon alkoxide component that forms a desired silica coating) is added, the aluminum pigment is retained in the coating forming composition for a predetermined time, the silicon alkoxide component is consumed, and the silica coating is deposited. By taking out the silica-coated aluminum pigment out of the system and subsequently adding a silicon alkoxide component, the composition can be used for depositing a film on the next aluminum particles, thereby providing a continuous process with high productivity. I found that I could build
[0031]
It is preferable that the silicon alkoxide be introduced at a rate as low as possible over time. When a predetermined amount of silicon alkoxide is injected at once, silica nuclei are generated by uniform nucleation in the liquid, which adheres to the surface of the aluminum particles, and the barrier property of the silica film is significantly reduced. On the other hand, when silicon alkoxide is introduced at a low speed, the barrier property of the film is improved, but it is not preferable in terms of productivity. Therefore, the introduction speed of silicon alkoxide may be determined in consideration of film physical properties and productivity. When a specific example is given, in a state where aluminum particles in the film forming composition are 7% by mass and a film is formed by using 10% by mass of silica with respect to the aluminum particles using tetraethoxysilane, tetraethoxysilane is used. The silane is added over 4 hours or more, preferably 8 hours or more, more preferably 12 hours or more.
[0032]
It is very important to control the deposition rate of the silica film when forming a film. The deposition rate of the film depends on the ratio of the organic solvent to water and the type of the organic solvent, but the maximum deposition rate during film formation is 3 nm / hr or less, more preferably 2 nm / hr or less, and still more preferably 1 nm / hr or less. It is to be.
[0033]
The deposition rate of the silica film is determined by extracting aluminum particles during film formation and measuring the thickness with a transmission electron microscope or the like. Alternatively, it is also possible to immerse a flat base material such as a silicon wafer in the film-forming composition and determine the film thickness with a step gauge.
[0034]
The deposition rate of the silica film will be described in detail. When considering the deposition rate, the concentration of silicic acid in the film-forming composition is important. It is important to keep the silicic acid concentration below the homogeneous nucleation region of silica. When silica particles are generated by uniform nucleation, they adhere to the aluminum pigment, and the barrier properties of the film are significantly reduced. Most ideally, the silica concentration is maintained in the heterogeneous nucleation region and the silica film is 2 It is preferable to stack one molecule at a time, but a higher deposition rate is desired from the viewpoint of productivity. In practice, the deposition rate is determined in consideration of the balance between film performance and productivity.
[0035]
Silicic acid concentration is determined by the supply rate and consumption rate of silicic acid. The supply rate is related to the supply rate and hydrolysis rate of the silicon alkoxide. Further, the hydrolysis rate is determined by the type and concentration of the catalyst, the temperature of the film forming composition, the amount of water, the amount of the organic solvent, the type and concentration of the Si-containing compound, and the like. The consumption rate is determined by the rate of polycondensation of the silicic acid, the surface area of the substrate, and the like.
[0036]
The temperature of the film-forming composition during the film-forming reaction is not particularly limited, but is preferably in the range of 10 ° C to 100 ° C, more preferably 20 ° C to 50 ° C. As the film formation temperature increases, the film formation rate increases. However, if the film formation temperature is too high, it becomes difficult to keep the solution composition constant due to volatilization of the components in the composition.
[0037]
When the solid / liquid separation is performed after the formation of the coating, a general separation method such as filtration, centrifugal sedimentation, and centrifugation can be used. If necessary, after the solid / liquid separation, it is preferable to suspend the silica-coated aluminum pigment in an organic solvent and perform a heat treatment to promote the dehydration-condensation of the silica to form a dense and strong film. In this case, dehydration and condensation of the silica proceed when heat treatment is performed at a temperature as high as possible for a long time. Therefore, the boiling point of the organic solvent used is preferably 70 ° C. or higher, more preferably 100 ° C. or higher. Further, a hydrophilic organic solvent having a high boiling point can be used in the composition for forming a silica film. In this case, the composition for forming a silica film after the film formation contains water, an organic solvent, a hydrolysis catalyst, and an alcohol by-produced from the silicon alkoxide. It is also possible to raise the boiling point, densify the silica coating by heat treatment, and perform solid-liquid separation. For example, propylene glycol monomethyl ether, water, using a composition for forming a silica film of ammonia, when tetraethoxysilane is used as a silica source, after substantially removing water, ethanol, and ammonia from the system by distillation under reduced pressure, Heat treatment can be performed.
[0038]
When the cut surface of the silica-coated aluminum pigment obtained by the above method is observed with a transmission electron microscope, it is observed that a silica coating is formed on the surface of the aluminum particles. It is difficult to measure the thickness of the coating accurately, but in the range of 3 nm to 30 nm. It is also observed that an aluminum oxide film is interposed between the surface of the aluminum particles and the silica coating. An aluminum oxide coating is usually present at about 4-6 nm.
[0039]
The silica-coated aluminum pigment obtained by the above method is 1150 to 1250 cm -1 And 1000-1100cm -1 Ratio of the absorbance of the absorption peak of the infrared absorption spectrum I (I = I 1 / I 2 : I 1 Is 1150-1250cm -1 Peak intensity (absorbance) of I, I 2 Is 1000-1100cm -1 Is 0.2 or more, preferably 0.3 or more, and more preferably 0.4 or more. The silica-coated aluminum pigment does not transmit infrared light in the transmission method using a KBr tablet, and the infrared absorption spectrum is distorted by the reflection of aluminum in the diffuse reflection method. Therefore, a film other than the aluminum pigment, which does not interfere with the analysis, for example, titanium oxide is applied to the film and the infrared absorption spectrum is measured.
[0040]
Usually, a silica film obtained by firing by a sol-gel method or the like, or obtained by a CVD method is 1150 to 1250 cm. -1 And 1000-1100cm -1 Is generally less than 0.2. It is known that the value of I generally changes the chemical bond or the functional group by calcination, and changes the hydrophilicity and oil absorbing properties of the silica coating.
[0041]
The silica coating of the silica-coated aluminum pigment of the present invention preferably has a refractive index of 1.435 or more, more preferably 1.440 or more. If the refractive index is less than 1.435, the denseness is low, which is not preferable. Further, the silica coating obtained without baking by the usual sol-gel method has a refractive index of less than 1.435, has a low density, and is not practical. Here, it is generally considered that the fineness and the refractive index of the silica coating have a positive correlation. (For example, C. JEFFERY BLINKER, SOL-GEL SCIENCE, 581-583, ACADEMIC PRESS (1990))
The refractive index is measured using a silica film formed on a silicon wafer that is simultaneously immersed in a composition for forming a silica film when synthesizing a silica-coated aluminum pigment. That is, it is considered that the same silicon film as the aluminum pigment is formed on the silicon wafer. The refractive index of the silica coating on the silicon wafer can be measured with an ellipsometer (manufactured by ULVAC; LASER ELLIPSOMETER ESM-1A).
[0042]
The surface of the aluminum pigment coated with the silica multilayer film of the present invention has a hydrophilic characteristic due to the properties of the silica. Therefore, when it is blended in a water-based paint or ink, it has a feature of good dispersibility. However, in some applications, it is preferable that the surface is hydrophobic. In that case, by performing a surface treatment with a silane-based, aluminum-based, or titanate-based coupling agent, the surface is chemically bonded to the surface to form an organic film, so that the surface can be modified to be hydrophobic. .
[0043]
The coupling agent to be used is not particularly limited, and may be one that is widely used for industrial purposes or as a reagent. Preferably, a silane coupling agent, an aluminum coupling agent, or a titanate coupling agent can be used. For example, as a silane coupling agent, a general formula RSix 3 (R: vinyl, glycidoxy, methacryl, amino, mercapto group, X: halogen, alkoxy group), an aluminum-based coupling agent (alkyl acetoacetate) aluminum diisopropylate, a titanate-based coupling agent, Examples include isopropyl triisostearoyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and isopropyl tri (N-aminoethyl-aminoethyl) titanate.
[0044]
The aluminum pigment coated with the silica film of the present invention can be used by blending it into a known and commonly used paint or ink composition. These paints and ink compositions may be not only water-based (emulsion, water-soluble) but also oil-based. Further, not only one-liquid type but also two or more liquids may be used as a mixture or may be accompanied by a reaction.
[0045]
Further, the paint and ink composition containing the aluminum pigment coated with the silica film of the present invention can contain other pigments and dyes according to the hue of the target paint and ink composition. However, it is desirable to use the pigment within a range that does not impair the metallic feeling of the aluminum pigment coated with the silica film of the present invention.
[0046]
The solvent used for the paint and ink composition containing the aluminum pigment coated with the silica film of the present invention is a variety of lipophilic, hydrophilic, and water-soluble solvents (including water) depending on the type of the paint and the ink composition. Can be used. Further, the solvent may be a mixture of a plurality of types depending on its function (thinner, retarder, leveling agent, etc.), or may be solventless.
[0047]
As the binder, various natural or synthetic polymers, monomers, oligomers, prepolymers, and the like can be used. In the case of a reactive paint or ink composition, a catalyst, an initiator, a crosslinking agent, a curing agent and the like can be contained.
[0048]
Further, the paint and ink composition containing the aluminum pigment coated with the silica film of the present invention can contain various additives as necessary. Examples include surfactants, stabilizers, preservatives, plasticizers, desiccants, pigment wetting agents, pigment dispersants, anticorrosives, flow regulators, fungicides, and ultraviolet absorbers.
[0049]
【Example】
Hereinafter, the present invention will be described more specifically by showing typical examples. These are merely examples for explanation, and the present invention is not limited to these.
(Example 1)
76 g of an aluminum paste Sap FM4010 (aluminum content: 67% by mass) manufactured by Showa Aluminum Powder Co., Ltd. was placed in a glass beaker, and dispersed in 724 g of propylene glycol monomethyl ether. The temperature was kept at 30 ° C. 13.2 g of tetraethoxysilane is diluted with 13.2 g of propylene glycol monomethyl ether, and this solution is dropped into the aluminum powder slurry over 12 hours at a constant rate so that the maximum deposition rate of the silica film is 1 nm / hr or less. Then, a film was formed. After dropping, stirring was continued for 12 hours, and the temperature was kept at 30 ° C. Thereafter, the mixture was filtered, and the filter cake was washed with propylene glycol monomethyl ether. Then, propylene glycol monomethyl ether was added to the filtrate to obtain a propylene glycol monomethyl ether paste containing 50% by mass of aluminum solids. In the electron microscope image, it is observed that the aluminum particles are covered by the dense and continuous silica film (FIGS. 1 and 2). The silica multilayer thickness was 8 nm. The refractive index of the silica film was 1.443, and the intensity ratio I of the infrared absorption spectrum of the silica film formed on titanium oxide coated with the silica film under the same conditions was 0.45.
(Example 2)
50 g of the propylene glycol monomethyl ether aluminum paste obtained in Example 1 was placed in a separable flask, and 420 g of propylene glycol monomethyl ether was added thereto. A reflux tube was attached to the upper part, and reflux was performed in propylene glycol monomethyl ether for 3 hours. After the completion of the reflux, the mixture was filtered, and propylene glycol monomethyl ether was added to the filtrate to obtain a propylene glycol monomethyl ether paste containing 50% by mass of aluminum solids. The refractive index of the silica film was 1.445, and the intensity ratio I of the infrared absorption spectrum of the silica film formed on titanium oxide coated with the silica film under the same conditions was 0.46.
(Example 3)
Take 10 g of the propylene glycol monomethyl ether paste obtained in Example 2, add 2 g of an aluminum-based coupling agent AL-M (manufactured by Ajinomoto Fine-Techno) diluted to 5% by mass with propylene glycol monomethyl ether, and add a spatula. And mixed well. After the treatment, the mixture was filtered, and propylene glycol monomethyl ether was added to the filtrate to obtain a propylene glycol monomethyl ether paste containing 50% by mass of aluminum solids.
(Comparative Example 1)
Example 1 was repeated except that tetraethoxysilane was added at one time.
(Comparative Example 2)
Example 1 was repeated except that 3.4 g of tetraethoxysilane was used instead of 13.2 g of tetraethoxysilane. Observation by a transmission electron microscope of the obtained aluminum pigment revealed that the thickness of the silica multilayer film was 2.1 nm.
(Comparative Example 3)
A paste was obtained in the same manner as in Example 1, except that 13.2 g of tetraethoxysilane was not used and was not added.
(Comparative Example 4)
76 g of aluminum paste Sap FM4010 (aluminum content: 67% by mass) manufactured by Showa Aluminum Powder Co., Ltd. was placed in a glass beaker, dispersed in 200 g of propylene glycol monomethyl ether, and 14.9 g of tetraethoxysilane was added. Under stirring, 21 g of 29 mass% ammonia water and 378 g of water were added, the liquid temperature was maintained at 30 ° C., and stirring was continued for 5 hours, followed by filtration. The filter cake was washed with propylene glycol monomethyl ether, and the filtrate was filtered. Was added to obtain a paste of propylene glycol monomethyl ether containing 50% by mass of aluminum solids. In the electron microscope image, it is observed that the silica fine particles adhere to the entire surface of the aluminum particles (FIG. 3).
(Examples 4 to 6, Comparative Examples 5 to 8)
Using the aluminum pigment pastes produced in Examples 1 to 3 and Comparative Examples 1 to 4, metallic paints were produced as follows, and Examples 4 to 6 and Comparative Examples 5 to 8 were made.
[0050]
5.8g aluminum pigment paste
5.8 g of ethyl acetate
And pre-dispersed, then
Origin Electric Planet SV Clear (acrylic lacquer) 37.5g
Origin Electric Planet Thinner # 175 70.0g
And stir for 5 minutes.
(Method of evaluating aluminum pigment)
The aluminum pigments obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were evaluated by the following methods. Table 1 shows the results of the evaluation test.
(1) Film thickness measurement
The silica-coated aluminum pigment was observed by a transmission electron microscope (JEM2010, manufactured by JEOL Ltd., accelerating voltage: 200 V), and the silica coating on the particle surface (a thin contrast that was recognized as covering the substrate with respect to the substrate) was observed. The thickness of the film portion) was measured by observation.
(2) IR spectrum measurement
The infrared absorption spectrum of the silica film was measured by coating FT-IR-8000 (manufactured by JASCO Corporation) on titanium oxide (manufactured by Showa Titanium, Super Titania F-1) coated with silica using the KBr method. 1150-1250cm -1 And 1000-1100cm -1 , The absorbance of the absorption peak was calculated from the transmittance of the infrared absorption spectrum at 1 / I 2 : I 1 Is 1150-1250cm -1 Absorbance of absorption peak of I 2 Is the absorbance of the absorption peak at 1000 to 1100 cm-1).
(3) Refractive index measurement
Using a silica film formed on a silicon wafer immersed in the system when synthesizing the silica-coated aluminum pigment, the measurement was carried out using an ellipsometer (manufactured by ULVAC; LASSER ELLIPSOMETER ESM-1A).
(4) Measurement of Si content
The aluminum paste was dried, dissolved in aqua regia, diluted with distilled water, and measured by ICP (plasma emission spectrometry) in which a calibration curve was drawn with an aqueous solution having a known Si concentration.
(5) Hydrogen gas generation test
In a test tube, 3 g of aluminum paste and 3 g of distilled water were added, and 14 g of an acrylic emulsion paint (E-208 manufactured by Mitsui Chemicals) was further added and stirred well to prepare an aqueous paint. The test tube was plugged with a gas collector, placed in a constant temperature water bath at 50 ° C., and the accumulated amount of hydrogen gas for two weeks (336 hours) was measured. The measurement was performed for each of the four samples.
(6) Gelation test
12 g of aluminum paste was placed in a brown glass bottle, and 48 g of a urethane acrylate UV-curable ink (manufactured by Jujo Chemical, Lake Cure LP4700) was added. I checked the condition. The result was evaluated as a three-stage evaluation of thickening (not gelling) and gelling without gelling. In addition, the degree of gelation is bad in this order.
(Evaluation method of paint containing aluminum pigment)
The coating materials obtained in Examples 4 to 6 and Comparative Examples 5 to 8 were evaluated by the following methods. Table 2 shows the results of the evaluation test.
(7) Painting of paint containing aluminum pigment
Using an Iwata spray gun WA-100, an automatic coating machine made by Kansai Paint was spray-coated on an ABS resin plate to a dry film thickness of 15 μm, and dried in an air oven at 60 ° C. for 20 minutes. A coated plate was obtained.
(8) Withstand voltage test
The aluminum pigment-containing coating applied to the ABS plate by the method of (7) was applied to the coating at an interval of 1 kV at a breaking current of 0.5 mA and an electrode interval of 10 mm using a withstand voltage measuring device (TW-516 manufactured by Tama Denso). Was applied for 20 seconds, and the maximum voltage at which the circuit was not interrupted by dielectric breakdown was defined as the withstand voltage.
(9) Gloss (metallic feeling)
The appearance of the coating film applied to the ABS plate was visually observed. The metallic luster was evaluated in three grades: excellent, good, and acceptable. The metallic luster is inferior in the order of excellent, good, and acceptable.
[0051]
[Table 1]
[0052]
[Table 2]
[0053]
【The invention's effect】
Silica multilayer coated aluminum pigment coated with a silica thin film multilayer film obtained in the present invention has excellent storage stability when blended in water-based paint, heat-curable, energy ray-curable paint, An object of the present invention is to provide an aluminum pigment whose voltage resistance and gloss (metallic feeling) are not deteriorated.
[0054]
In addition, the water-based paint or water-based ink containing the aluminum pigment coated with the silica multilayer film of the present invention has a volume of hydrogen gas of 10 cm per 1 g of aluminum in the aluminum pigment at 50 ° C. for 336 hours. 3 Below, further 6cm 3 Below, 1cm if better 3 The amount of hydrogen gas is smaller than that of a conventional water-based paint or water-based ink containing a conventional silica-coated aluminum pigment, and the stability is excellent.
[0055]
[Brief description of the drawings]
FIG. 1 is a scanning electron micrograph (magnification: 30,000 times) of the aluminum pigment obtained in Example 1.
FIG. 2 is a transmission electron micrograph (1 × 10 magnification) showing a cross section of the aluminum pigment obtained in Example 1. 6 Times)
FIG. 3 is a scanning electron micrograph (× 30,000) of the aluminum pigment obtained in Comparative Example 4.
[Explanation of symbols]
1 Silica film
2 Aluminum oxide coating
3 Aluminum particles

Claims (25)

  1. A silica-coated aluminum pigment comprising a silica thin film having a thickness of 0.5 to 5 nm formed in multiple layers on the surface of aluminum particles.
  2. The silica-coated aluminum pigment according to claim 1, wherein the aluminum pigment has an aluminum oxide layer between the surface of the aluminum particles and the silica thin film.
  3. The silica-coated aluminum pigment according to claim 1 or 2, wherein the silica multilayer film in which the silica thin film is formed in multiple layers has a thickness of 3 to 30 nm.
  4. The volume of hydrogen gas generated from 1 g of aluminum in the aluminum pigment when mixed with an aqueous paint or an aqueous ink at 50 ° C. for 336 hours is 1 cm 3 or less. Or a silica-coated aluminum pigment.
  5. The volume of hydrogen gas generated per 1 g of aluminum in the aluminum pigment when mixed with an aqueous paint or an aqueous ink at 50 ° C. for 336 hours is 10 cm 3 or less. Or a silica-coated aluminum pigment.
  6. The ratio of the absorption peak intensity of the infrared absorption spectrum in 1150~1250Cm -1 and 1000~1100Cm -1 silica multilayer film I (I = I 1 / I 2: absorption peak intensity I 1 is 1150~1250cm -1, I 2 is an absorption peak intensity of 1000 to 1100 cm -1 ) is 0.2 or more, and the refractive index of the silica film is 1.435 or more, 6. Silica-coated aluminum pigment.
  7. The silica-coated aluminum pigment according to any one of claims 1 to 6, wherein the amount of Si element in the silica multilayer film is 1 to 10% by mass based on aluminum in the aluminum particles.
  8. The silica-coated aluminum pigment according to any one of claims 1 to 7, wherein the surface of the silica multilayer film is hydrophobized with a hydrophobicity imparting agent.
  9. The silica-coated aluminum pigment according to claim 8, wherein the hydrophobicity imparting agent is at least one selected from a silane coupling agent, an aluminum coupling agent, and a titanate coupling agent.
  10. The silica-coated aluminum pigment according to any one of claims 1 to 9, wherein the aluminum particles are flake-like particles.
  11. The silica-coated aluminum pigment according to any one of claims 1 to 9, wherein the aluminum particles are flake-shaped particles, the average particle diameter D50 is 5 to 100 µm, and the aspect ratio (particle diameter / thickness) is 20 or more.
  12. Dispersing the aluminum particles in a solution containing a hydrolysis catalyst, water and a hydrophilic organic solvent, and adding a solution containing a Si-containing compound to the dispersion at a maximum deposition rate of the silica film of 3 nm / hr or less. For producing a silica-coated aluminum pigment containing silica.
  13. Dispersing the aluminum particles in a solution containing a Si-containing compound, water and a hydrophilic organic solvent, and adding a solution containing a hydrolysis catalyst to the dispersion at a maximum deposition rate of the silica film of 3 nm / hr or less. For producing a silica-coated aluminum pigment containing silica.
  14. The method for producing a silica-coated aluminum pigment according to claim 12 or 13, further comprising a step of heating the silica-coated aluminum pigment in a solution containing an organic solvent having a boiling point of 70 ° C or higher.
  15. The method for producing a silica-coated aluminum pigment according to any one of claims 12 to 14, wherein the Si-containing compound is a compound capable of hydrolyzing in the presence of a hydrolysis catalyst to produce silica.
  16. The method for producing a silica-coated aluminum pigment according to claim 15, wherein the Si-containing compound is a silicon alkoxide.
  17. The silica-coated aluminum pigment according to claim 16, wherein the silicon alkoxide is at least one selected from tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane. Production method.
  18. The silica coating according to any one of claims 12 to 14, wherein the hydrolysis catalyst is at least one selected from ammonia, ethylenediamine, ammonium carbonate, ammonium bicarbonate, ammonium formate, ammonium acetate, sodium carbonate, and sodium bicarbonate. A method for producing an aluminum pigment.
  19. A paste comprising the silica-coated aluminum pigment according to claim 1.
  20. An aqueous paste containing the silica-coated aluminum pigment according to any one of claims 1 to 11, and water.
  21. A coating film comprising the silica-coated aluminum pigment according to claim 1.
  22. A paint containing the silica-coated aluminum pigment according to claim 1.
  23. An ink composition containing the silica-coated aluminum pigment according to any one of claims 1 to 11.
  24. A coated article to which the paint according to claim 22 has been applied.
  25. A printed matter using the ink composition according to claim 23.
JP2003202191A 2002-07-31 2003-07-28 Silica-coated aluminum pigment and its production method as well as application thereof Pending JP2004124069A (en)

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